US6720280B2 - Dielectric composition for high frequency resonators - Google Patents

Dielectric composition for high frequency resonators Download PDF

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US6720280B2
US6720280B2 US10/170,413 US17041302A US6720280B2 US 6720280 B2 US6720280 B2 US 6720280B2 US 17041302 A US17041302 A US 17041302A US 6720280 B2 US6720280 B2 US 6720280B2
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dielectric
dielectric material
bmn
resonance
high frequency
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Katsuya Yamagiwa
Jun Otsuka
Takashi Kasashima
Manabu Sato
Kazuhisa Itakura
Takashi Oba
Masahiko Matsumiya
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Niterra Co Ltd
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NGK Spark Plug Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • C04B35/457—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates based on tin oxides or stannates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C01G33/006—Compounds containing, besides niobium, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/36—Three-dimensional structures pyrochlore-type (A2B2O7)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • This invention relates to a dielectric material suitable for use as a dielectric resonator. More particularly, the invention relates to a low loss dielectric material suitable for use as a high frequency dielectric resonator.
  • BMN system Materials of the BaO—MgO—Nb 2 O 5 system (referred to herein as the BMN system) are known as high frequency dielectric materials.
  • Laid-Open Japanese Patent Application No. 60-124305 and Japanese Patent Publication No. 2-60628 describe materials of the BMN system suitable for high frequency use.
  • the BMN system materials exemplified in the above Japanese patent documents include Ta which is expensive. In order to reduce manufacturing costs, it would be desirable to provide a BMN system material containing no Ta but still having desirable high frequency characteristics.
  • the present invention has as an object thereof to provide a dielectric composition which is based on a BMN system material but which includes no Ta, and in which: (1) the dielectric constant ⁇ is about 30, (2) the Q-value, i.e., the no-load quality coefficient, is large, and (3) the absolute value of ⁇ f , the temperature coefficient of the resonant frequency, is comparatively small.
  • the parameters Q (sometimes given as Q 0 ) and ⁇ f are important quantities in analyzing the characteristics of a dielectric material, with the latter being determined by measuring the change in resonant frequency with temperature.
  • a dielectric material having a composite perovskite crystal structure including K, Ba, Mg and Nb as metallic elements in a main crystal phase, and having a compositional formula represented by:
  • a dielectric material having a composite perovskite crystal structure including K, Mg, Sb, Ba and Nb as metallic elements in the main crystal phase, and having a compositional formula represented by:
  • a dielectric material having of a composite perovskite crystal structure including Sn, K, Mg, Sb, Ba and Nb as metallic elements in a main crystal phase, and having a compositional formula represented by:
  • the oxygen ratios will naturally depend upon the variables ⁇ , ⁇ , ⁇ , ⁇ , and p. Accordingly, none of the dielectric compositions of the present invention should be considered as being limited only to an oxygen mole ratio of 3. This is because the most important aspect of the dielectric compositions of the present invention is not whether the mole ratio of oxygen is 3, but, instead, whether the mole ratio of each different metal is prescribed within a certain range. Accordingly, in the dielectric compositions of the present invention, it should be noted that the mole ratio of oxygen is given as 3 for the convenience of avoiding unnecessary complexity in the compositional formulas.
  • the dielectric compositions of the present invention are characterized in that sintering can be improved without any deterioration of the high frequency characteristics, by adding K p NbO 3 to a specific BMN system material and optionally incorporating a predetermined amount of another specified metal in a specific ratio.
  • a higher Q-value can be obtained by prescribing the quantity of Ba occupying Ba sites within the composite perovskite compound, to a predetermined range.
  • the coefficient ⁇ of Ba is preferably set to be within the range from 0.9 to 1.3. When ⁇ is greater than 1.3, it is difficult to sinter the BMN system material. When ⁇ is smaller than 0.9, the Q-value is reduced.
  • the coefficient ⁇ preferably ranges from 1.0 to 1.2, and, more preferably, ranges from 1.0 to 1.05.
  • the temperature coefficient ( ⁇ f ) of the resonance frequency can preferably also be set as well as the Q-value.
  • the coefficient ⁇ of Mg preferably ranges from 0.3 to 0.35. When ⁇ is greater than 0.35, it is difficult to sinter the BMN system material. When ⁇ is smaller than 0.3, the Q-value is reduced.
  • the temperature coefficient ( ⁇ f ) of the resonant frequency can preferably also be set as well as the Q-value.
  • a higher Q-value can be obtained by using a material (referred to herein as a BMNSb material) in which an Nb site in the dielectric composition of the present invention is partially replaced with Sb.
  • the coefficient ⁇ of Sb is preferably set to be equal to or smaller than 0.125. When ⁇ is greater than 0.125, sintering is more difficult and the reproducibility of the desirable characteristics is also reduced.
  • the coefficient ⁇ more preferably ranges from 0.05 to 0.075 since a high Q-value can then be obtained.
  • the temperature coefficient ( ⁇ f ) of the resonance frequency (which can approach zero) can be further improved by partially replacing the B-site of the perovskite crystal structure with Sn in the BMNSb system material.
  • the quantity y of Sn preferably ranges from 0.15 to 0.3 since the temperature coefficient ⁇ f can be adjusted to within ⁇ 10.
  • An excellent value almost near 0 ppm/K in the temperature coefficient ⁇ f is obtained by setting the quantity y of Sn to be within the range of 0.22 to 0.23 (and, more preferably, at 0.225).
  • the quantities of commercially available BaCO 3 , MgO, Nb 2 O 5 , Sb 2 O 3 and K 2 CO 3 represented by the corresponding coefficients of x, y, ⁇ , ⁇ , ⁇ , ⁇ and p, as shown in the following Table 1, and ethanol as a solvent, are wet-blended.
  • the blended powder which is obtained by drying and removing the solvent, is then calcined for two hours at 1100° C. in air.
  • a wax system binder, a dispersion agent and ethanol are added to the calcined material, and are crushed and mixed by a ball mill so that a slurry is obtained.
  • This slurry is dried and granulated, and the granulated powder is molded in a column 19 mm in diameter and 12 mm in thickness at a pressure of 10 to 20 MPa.
  • This molded body is then processed by a CIP (cold hydrostatic press) at a pressure of 150 MPa. Finally, this CIP-processed molded body is heated for four hours at 1550 to 1650° C. in air to form a calcined body.
  • the calcined body obtained as described above is formed into a column (14 mm in diameter and 7 mm in height) and surface finished with a surface grinder.
  • the dielectric constant ⁇ , the quantity Qf, which is the product of the Q-value and the resonance frequency f, and the temperature coefficient ⁇ f of the resonance frequency (wherein the measurement frequency is 4 to 6 GHz, and the temperature range is 25 to 80° C.) are measured using the known parallel conductor plate type dielectric resonator method. The results are set out in Table 2.
  • the dielectric constant ⁇ is about 30, the value of Qf is advantageously high and the temperature coefficient ⁇ f of the resonance frequency has a small value in the range of ⁇ 25 ppm/K.
  • the dielectric materials of the present invention have a high Q-values and are able to be used for high frequency purposes but include no expensive Ta. Further, the materials have dielectric constants of about 30 and have reduced absolute values of the temperature coefficient ⁇ f of the resonance frequency. Moreover, dielectric materials having such excellent high frequency characteristics can be obtained without using special powder processes or sintering methods.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
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  • Structural Engineering (AREA)
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  • Compositions Of Oxide Ceramics (AREA)

Abstract

A dielectric composition is based on a BaO—MgO—Nb2O5 system material (BMN system material) having a dielectric constant, ε, of about 30, a large Q-value (no-load quality coefficient) and a comparatively small absolute value of the temperature coefficient (τf) of its resonance frequency but containing no expensive Ta. The dielectric material has a composite perovskite crystal structure as the main crystal phase, wherein a predetermined amount of KNbO3 is added to a BMN system material. The high frequency characteristics can be further improved by partially replacing Nb with Sb and partially replacing the B site of the perovskite crystal structure with Sn.

Description

FIELD OF THE INVENTION
This invention relates to a dielectric material suitable for use as a dielectric resonator. More particularly, the invention relates to a low loss dielectric material suitable for use as a high frequency dielectric resonator.
BACKGROUND OF THE INVENTION
Materials of the BaO—MgO—Nb2O5 system (referred to herein as the BMN system) are known as high frequency dielectric materials. Laid-Open Japanese Patent Application No. 60-124305 and Japanese Patent Publication No. 2-60628 describe materials of the BMN system suitable for high frequency use.
However, the BMN system materials exemplified in the above Japanese patent documents include Ta which is expensive. In order to reduce manufacturing costs, it would be desirable to provide a BMN system material containing no Ta but still having desirable high frequency characteristics.
SUMMARY OF THE INVENTION
The present invention has as an object thereof to provide a dielectric composition which is based on a BMN system material but which includes no Ta, and in which: (1) the dielectric constant ε is about 30, (2) the Q-value, i.e., the no-load quality coefficient, is large, and (3) the absolute value of τf, the temperature coefficient of the resonant frequency, is comparatively small. As will be understood by those skilled in the art, the parameters Q (sometimes given as Q0) and τf are important quantities in analyzing the characteristics of a dielectric material, with the latter being determined by measuring the change in resonant frequency with temperature.
In accordance with a first aspect of the present invention, there is provided a dielectric material having a composite perovskite crystal structure including K, Ba, Mg and Nb as metallic elements in a main crystal phase, and having a compositional formula represented by:
(1−x)Baα(MgβNb1−β)O3−xKpNbO3.
wherein x, α, β and p have values satisfying the conditions
0<x≦0.1, 0.9≦α≦1.3, 0.3≦β≦0.35 and 1≦p≦2.
In accordance with a second aspect of the present invention, there is provided a dielectric material having a composite perovskite crystal structure including K, Mg, Sb, Ba and Nb as metallic elements in the main crystal phase, and having a compositional formula represented by:
(1−x)Baα(MgβNbγSbδ)O3−xKpNbO3,
wherein x, α, β, γ, δ and p have values satisfying the conditions
0<x≦0.1, 0.9≦α≦1.3, 0.3≦β≦0.35, 0<δ≦0.125, β+γ+δ=1 and 1≦p≦2.
In accordance with a third aspect of the present invention, there is provided a dielectric material having of a composite perovskite crystal structure including Sn, K, Mg, Sb, Ba and Nb as metallic elements in a main crystal phase, and having a compositional formula represented by:
(1−x){(1−y)Baα(MgβNbγSbδ)O3-yBaSnO3}-xK pNbO3
wherein x, y, α, β, γ, δ and p have values satisfying the conditions
0<x≦0.1, 0<y≦0.5, 0.9≦α≦1.3, 0.3≦β≦0.35, 0<δ≦0.125, δ+γ+δ=1 and 1≦p≦2.
Further features and advantages of the present invention will be set forth in, or apparent from, the detailed description of preferred embodiments thereof which follows.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the compositional formulas set forth above, the oxygen ratios will naturally depend upon the variables α, β, γ, δ, and p. Accordingly, none of the dielectric compositions of the present invention should be considered as being limited only to an oxygen mole ratio of 3. This is because the most important aspect of the dielectric compositions of the present invention is not whether the mole ratio of oxygen is 3, but, instead, whether the mole ratio of each different metal is prescribed within a certain range. Accordingly, in the dielectric compositions of the present invention, it should be noted that the mole ratio of oxygen is given as 3 for the convenience of avoiding unnecessary complexity in the compositional formulas.
The dielectric compositions of the present invention are characterized in that sintering can be improved without any deterioration of the high frequency characteristics, by adding KpNbO3 to a specific BMN system material and optionally incorporating a predetermined amount of another specified metal in a specific ratio.
When no KpNbO3 is added, the specific BMN (BaO—MgO—Nb2O5) system material cannot be sintered. Further, when the amount, x, of KpNbO3 is greater than 0.1, the Q-value (the no-load quality coefficient) is reduced. Thus, the sintering and dielectric characteristics can be reconciled by prescribing the ratio of KpNbO3 to BMN (BaO—MgO—N b2O5) material as x.
When the coefficient p of KpNbO3 is smaller than 1, it is difficult to sinter the specific BMN system material. When the coefficient p of KpNbO3 is greater than 2, the Q-value is reduced.
A higher Q-value can be obtained by prescribing the quantity of Ba occupying Ba sites within the composite perovskite compound, to a predetermined range. Specifically, the coefficient α of Ba is preferably set to be within the range from 0.9 to 1.3. When α is greater than 1.3, it is difficult to sinter the BMN system material. When α is smaller than 0.9, the Q-value is reduced. The coefficient α preferably ranges from 1.0 to 1.2, and, more preferably, ranges from 1.0 to 1.05. The temperature coefficient (τf) of the resonance frequency can preferably also be set as well as the Q-value.
The coefficient β of Mg preferably ranges from 0.3 to 0.35. When β is greater than 0.35, it is difficult to sinter the BMN system material. When β is smaller than 0.3, the Q-value is reduced. The coefficient β more preferably ranges from 0.31 to 0.33. The temperature coefficient (τf) of the resonant frequency can preferably also be set as well as the Q-value.
A higher Q-value can be obtained by using a material (referred to herein as a BMNSb material) in which an Nb site in the dielectric composition of the present invention is partially replaced with Sb. The coefficient δ of Sb is preferably set to be equal to or smaller than 0.125. When δ is greater than 0.125, sintering is more difficult and the reproducibility of the desirable characteristics is also reduced. The coefficient δ more preferably ranges from 0.05 to 0.075 since a high Q-value can then be obtained.
The temperature coefficient (τf) of the resonance frequency (which can approach zero) can be further improved by partially replacing the B-site of the perovskite crystal structure with Sn in the BMNSb system material. The quantity y of Sn preferably ranges from 0.15 to 0.3 since the temperature coefficient τf can be adjusted to within ±10. An excellent value almost near 0 ppm/K in the temperature coefficient τf is obtained by setting the quantity y of Sn to be within the range of 0.22 to 0.23 (and, more preferably, at 0.225).
The following Examples illustrate the invention but should not be considered as limiting the scope thereof.
EXAMPLES Manufacture of Dielectric Composition
The quantities of commercially available BaCO3, MgO, Nb2O5, Sb2O3 and K2CO3 represented by the corresponding coefficients of x, y, α, β, γ, δ and p, as shown in the following Table 1, and ethanol as a solvent, are wet-blended. The blended powder, which is obtained by drying and removing the solvent, is then calcined for two hours at 1100° C. in air. Next, a wax system binder, a dispersion agent and ethanol are added to the calcined material, and are crushed and mixed by a ball mill so that a slurry is obtained. This slurry is dried and granulated, and the granulated powder is molded in a column 19 mm in diameter and 12 mm in thickness at a pressure of 10 to 20 MPa. This molded body is then processed by a CIP (cold hydrostatic press) at a pressure of 150 MPa. Finally, this CIP-processed molded body is heated for four hours at 1550 to 1650° C. in air to form a calcined body.
Evaluation of Dielectric Characteristics
The calcined body obtained as described above is formed into a column (14 mm in diameter and 7 mm in height) and surface finished with a surface grinder. The dielectric constant ε, the quantity Qf, which is the product of the Q-value and the resonance frequency f, and the temperature coefficient τf of the resonance frequency (wherein the measurement frequency is 4 to 6 GHz, and the temperature range is 25 to 80° C.) are measured using the known parallel conductor plate type dielectric resonator method. The results are set out in Table 2.
TABLE 1
Composition
Sample No. x y α β γ δ P
1 0.100 0.000 1.000 0.320 0.630 0.050 1.000
2 0.100 0.000 1.000 0.320 0.630 0.050 1.250
3 0.075 0.000 1.000 0.320 0.630 0.050 1.250
4 0.025 0.000 1.000 0.300 0.650 0.050 1.250
5 0.050 0.000 1.000 0.334 0.589 0.077 1.000
6 0.050 0.000 1.000 0.334 0.589 0.077 1.000
7 0.025 0.000 1.000 0.350 0.600 0.050 1.250
8 0.025 0.000 1.000 0.308 0.642 0.050 1.250
9 0.025 0.000 1.000 0.320 0.579 0.101 1.250
10 0.025 0.000 1.000 0.320 0.630 0.050 2.000
11 0.025 0.000 1.000 0.350 0.600 0.050 1.250
12 0.025 0.000 1.000 0.349 0.622 0.000 1.250
13 0.025 0.000 1.000 0.309 0.616 0.075 1.250
14 0.025 0.000 1.000 0.320 0.670 0.010 1.250
15 0.025 0.000 1.000 0.349 0.592 0.059 1.250
16 0.050 0.000 1.000 0.320 0.630 0.050 1.250
17 0.025 0.000 1.300 0.320 0.630 0.050 1.250
18 0.025 0.000 1.000 0.320 0.555 0.125 1.250
19 0.025 0.000 1.000 0.326 0.623 0.050 1.250
20 0.010 0.000 1.000 0.320 0.630 0.050 1.250
21 0.025 0.000 1.000 0.345 0.579 0.075 1.250
22 0.025 0.000 1.000 0.320 0.630 0.050 1.000
23 0.025 0.000 1.000 0.340 0.610 0.050 1.250
24 0.025 0.000 1.200 0.320 0.630 0.050 1.250
25 0.025 0.000 1.000 0.317 0.658 0.025 1.250
26 0.025 0.000 1.000 0.338 0.595 0.067 1.250
27 0.025 0.000 1.000 0.342 0.595 0.064 1.250
28 0.025 0.000 1.000 0.320 0.580 0.100 1.250
29 0.025 0.000 1.000 0.334 0.616 0.050 1.250
30 0.025 0.000 1.000 0.344 0.632 0.025 1.250
31 0.025 0.000 1.000 0.320 0.630 0.050 1.250
32 0.025 0.000 1.100 0.320 0.630 0.050 1.250
33 0.025 0.000 1.000 0.320 0.630 0.050 1.500
34 0.025 0.000 1.000 0.320 0.650 0.030 1.250
35 0.025 0.000 1.000 0.317 0.633 0.050 1.250
36 0.025 0.000 1.000 0.325 0.600 0.075 1.000
37 0.025 0.000 1.000 0.333 0.597 0.070 1.250
38 0.025 0.000 1.000 0.320 0.605 0.075 1.250
39 0.005 0.000 1.000 0.317 0.610 0.073 1.250
40 0.005 0.000 1.000 0.317 0.610 0.073 1.250
41 0.025 0.000 1.000 0.323 0.600 0.077 1.250
42 0.025 0.000 1.000 0.325 0.600 0.075 1.250
43 0.025 0.000 1.025 0.317 0.633 0.050 1.250
44 0.025 0.150 1.025 0.317 0.633 0.050 1.250
45 0.025 0.190 1.025 0.317 0.633 0.050 1.250
46 0.025 0.200 1.025 0.317 0.633 0.050 1.250
47 0.025 0.225 1.025 0.317 0.633 0.050 1.250
48 0.025 0.250 1.025 0.317 0.633 0.050 1.250
49 0.025 0.300 1.025 0.317 0.633 0.050 1.250
50 0.025 0.400 1.025 0.317 0.633 0.050 1.250
51 0.025 0.500 1.025 0.317 0.633 0.050 1.250
52 0.000 0.000 1.000 0.320 0.630 0.050 1.250
53 0.125 0.000 1.000 0.320 0.630 0.050 1.250
54 0.025 0.000 1.000 0.320 0.630 0.050 0.800
55 0.100 0.000 1.000 0.320 0.630 0.050 0.800
56 0.025 0.000 0.950 0.320 0.630 0.050 1.250
57 0.025 0.000 1.400 0.320 0.630 0.050 1.250
58 0.025 0.000 1.000 0.234 0.666 0.101 1.250
59 0.025 0.000 1.000 0.250 0.600 0.150 1.250
60 0.025 0.000 1.000 0.267 0.633 0.099 1.250
61 0.025 0.000 1.000 0.283 0.667 0.050 1.250
62 0.025 0.000 1.000 0.283 0.642 0.075 1.250
63 0.025 0.000 1.000 0.284 0.617 0.150 1.250
64 0.025 0.000 1.000 0.290 0.660 0.050 1.250
65 0.025 0.000 1.000 0.299 0.650 0.050 1.250
66 0.025 0.000 1.000 0.299 0.600 0.101 1.250
67 0.025 0.000 1.000 0.320 0.680 0.000 1.250
68 0.025 0.000 1.000 0.320 0.530 0.150 1.250
69 0.025 0.000 1.000 0.332 0.639 0.000 1.250
70 0.025 0.000 1.000 0.360 0.590 0.050 1.250
71 0.025 0.000 1.000 0.374 0.600 0.025 1.250
72 0.025 0.000 1.000 0.374 0.600 0.025 1.250
73 0.025 0.600 1.025 0.317 0.633 0.050 1.250
TABLE 2
Characteristics
Water
absorption
coefficient
Sample No. [%] Dielectric constant Qf [GHz] τf [ppm/K]
1 <0.1 26.4 10879 22
2 <0.1 27.0 10993 25
3 <0.1 27.9 11927 24
4 <0.1 31.7 12318 20
5 <0.1 28.0 12841 24
6 <0.1 28.6 13055 23
7 <0.1 26.9 13099 19
8 <0.1 32.1 14206 24
9 <0.1 28.5 14271 24
10 <0.1 31.5 15049 23
11 <0.1 27.1 15217 22
12 <0.1 27.3 15224 18
13 <0.1 30.7 15381 20
14 <0.1 30.7 15723 22
15 <0.1 28.2 16201 20
16 <0.1 28.3 16222 21
17 <0.1 30.8 16247 18
18 <0.1 28.7 17216 24
19 <0.1 30.3 17224 21
20 <0.1 29.1 17320 18
21 <0.1 27.9 18273 25
22 <0.1 30.2 18902 23
23 <0.1 28.0 18903 21
24 <0.1 30.5 18957 19
25 <0.1 32.8 19242 24
26 <0.1 28.3 19746 23
27 <0.1 27.8 19900 20
28 <0.1 29.3 20723 21
29 <0.1 29.2 21010 18
30 <0.1 28.1 21132 16
31 <0.1 31.3 21895 20
32 <0.1 31.0 22006 21
33 <0.1 30.9 22015 23
34 <0.1 30.2 22017 21
35 <0.1 31.5 22169 26
36 <0.1 26.7 22345 23
37 <0.1 28.8 23017 21
38 <0.1 29.8 23519 23
39 <0.1 28.7 24373 16
40 <0.1 28.6 24830 15
41 <0.1 28.5 24943 22
42 <0.1 27.0 26824 22
43 <0.1 29.6 27031 17
44 <0.1 27.4 24048 6
45 <0.1 27.2 24143 3
46 <0.1 27.0 23351 3
47 <0.1 26.7 21717 1
48 <0.1 26.9 16300 4
49 <0.1 25.7 15232 −3
50 <0.1 25.1 12403 −8
51 <0.1 24.4 10082 −12
52 >0.1 — — —
53 <0.1 26.0  5279 25
54 >0.1 — — —
55 >0.1 — — —
56 <0.1 Very small Very small —
resonance resonance
57 >0.1 — — —
58 <0.1 Very small Very small —
resonance resonance
59 <0.1 Very small Very small —
resonance resonance
60 <0.1 Very small Very small —
resonance resonance
61 <0.1 Very small Very small —
resonance resonance
62 <0.1 Very small Very small —
resonance resonance
63 <0.1 Very small Very small —
resonance resonance
64 <0.1 Very small Very small —
resonance resonance
65 <0.1 32.1  5972 23
66 <0.1 29.3  7021 26
67 <0.1 31.2  7895 23
68 <0.1 28.3  3689 25
69 <0.1 28.9  9722 25
70 >0.1 — — —
71 >0.1 — — —
72 >0.1 — — —
73 <0.1 23.9  6051 −20
It can be seen from the results set out in Table 2 that for the dielectric compositions of the present invention, the dielectric constant ε is about 30, the value of Qf is advantageously high and the temperature coefficient τf of the resonance frequency has a small value in the range of ±25 ppm/K. No data, except for the water absorption coefficient, are shown for samples numbers 52, 54, 55, 57 and 70 to 72; no data measurements were taken for these samples because of a sintering defect.
The dielectric materials of the present invention have a high Q-values and are able to be used for high frequency purposes but include no expensive Ta. Further, the materials have dielectric constants of about 30 and have reduced absolute values of the temperature coefficient τf of the resonance frequency. Moreover, dielectric materials having such excellent high frequency characteristics can be obtained without using special powder processes or sintering methods.
This application is based on Japanese Patent Application No. 2001-187008, filed Jun. 20, 2001, which is incorporated herein by reference in its entirety.
While the invention has been described in detail and with reference to the specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (12)

What is claimed:
1. A dielectric material having a composite perovskite crystal structure including K, Ba, Mg and Nb as metallic elements in a main crystal phase and having a compositional formula represented by
(1−x)Baα(MgβNb1−β)O3-xKpNbO3,
wherein x, α, β and p have values satisfying the conditions
0<x≦0.1, 0.9≦α≦1.3, 0.3≦β≦0.35 and 1≦p≦2.
2. A dielectric material having a composite perovskite crystal structure including K, Mg, Sb, Ba and Nb as metallic elements in a main crystal phase and having a compositional formula represented by
(1−x)Baα(MgβNbγSbδ)O3-xKpNbO3,
wherein x, α, β, γ, δ and p have values satisfying the conditions
0<x≦0.1, 0.9 ≦α≦1.3, 0.3≦β≦0.35, 0<δ≦0.125, β+γ+δ=1 and 1≦p≦2.
3. A dielectric material having a composite perovskite crystal structure including Sn, K, Mg, Sb, Ba and Nb as metallic elements in a main crystal phase and having a compositional formula represented by
(1−x){(1−y)Baα(MgβNbγSbδ)O3-yBaSnO3}-xKpNbO3,
wherein x, y, α, β, γ, δ and p have values satisfying the conditions
0<x≦0.1, 0<y≦0.5, 0.9≦α≦1.3, 0.3≦β≦0.35, 0<δ≦0.125, β+γ+δ=1 and 1≦p≦2.
4. A dielectric material as claimed in claim 1 wherein 1.0≦α≦1.3.
5. A dielectric material as claimed in claim 4 wherein 1.0≦α≦1.2.
6. A dielectric material as claimed in claim 5 wherein 1.0≦α≦1.05.
7. A dielectric material as claimed in claim 2 wherein 1.0≦α≦1.3.
8. A dielectric material as claimed in claim 7 wherein 1.0≦α≦1.2.
9. A dielectric material as claimed in claim 8 wherein 1.0≦α≦1.05.
10. A dielectric material as claimed in claim 3 wherein 1.0≦α≦1.3.
11. A dielectric material as claimed in claim 10 wherein 1.0≦α≦1.2.
12. A dielectric material as claimed in claim 11 wherein 1.0≦α≦1.05.
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